Biopolymers have emerged as promising alternatives to traditional heavy metal–based radiation shielding materials due to their sustainability, low toxicity, high hydrogen content, and lightweight nature. Although conventional lead based systems provide high photon attenuation efficiency, issues such as toxicity, excessive weight, and limited processability significantly restrict their usability. In contrast, biopolymers such as cellulose, chitosan, starch, and polylactic acid (PLA) offer strong potential for neutron moderation owing to their hydrogen rich molecular structures, which enable effective elastic scattering of fast neutrons. To enhance photon shielding performance, these matrices are often hybridized with high atomic number (Z) fillers including Bi₂O₃, PbO₂, WO₃, ZnO, Fe₃O₄ or CdO, enabling simultaneous attenuation of gamma and neutron radiation within a single composite system. Recent experimental studies and Monte Carlo simulations have demonstrated that such hybrid biopolymer composites can achieve competitive mass attenuation coefficients (MAC), reduced half-value layer (HVL), and increased effective atomic numbers (Z_eff), comparable to or surpassing conventional lead-free commercial bismuth-epoxy systems. Advances in nanotechnology and additive manufacturing have further accelerated the development of multilayered, flexible, and multifunctional shielding architectures. Overall, biopolymer-based radiation shielding materials represent a transformative and environmentally sustainable approach for emerging applications in medical imaging and therapy, nuclear technology, aerospace structures, and lightweight personal protective equipment.